Polymerization catalyst for olefins and process for polymerization of olefins

ABSTRACT

Olefin polymers with a broad molecular weight distribution can be obtained while maintaining the high stereoregularity of the polymers by polymerizing olefins using a catalyst comprising (A) a solid catalyst component prepared by contacting (a) a dialkoxymagnesium, (b) a tetravalent titanium halide compound, and (c) an electron donor compound one another, (B) an organoaluminum compound of the formula R 1   p AlQ 3-p , and (C) an aminosilane compound of the formula R 2 R 3 Si(OR 4 ) 2 .

TECHNICAL FIELD

[0001] The present invention relates to a catalyst for olefinpolymerization which can produce olefin polymers with a broad molecularweight distribution in a high yield while maintaining highstereoregularity of the olefin polymers and to a process forpolymerizing olefins.

BACKGROUND ART

[0002] Conventionally, a number of processes for polymerizing orcopolymerizing olefins in the presence of a catalyst for olefinpolymerization comprising a solid catalyst component containingmagnesium, titanium, an electron donor compound, and halogen as theessential components, an organoaluminum compound, and an organosiliconcompound have been proposed.

[0003] For example, Japanese Unexamined Patent Publication (hereinafterreferred to as JP-A) No. 63310/1982 and JP-A No. 63311/1982 propose amethod for polymerizing olefins with three or more carbon atoms, inwhich a combined catalyst comprising a solid catalyst componentcontaining a magnesium compound, a titanium compound, and an electrondonor, an organoaluminum compound, and an organosilicon compound havinga Si—O—C bond is used. However, because these methods are notnecessarily satisfactory for producing highly stereoregular polymers ina high yield, further improvement of these methods has been desired.

[0004] JP-A No. 3010/1988 proposes a catalyst for olefin polymerizationand a process for polymerizing olefins in the presence of the catalyst.The catalyst for olefin polymerization comprises a solid catalystcomponent, prepared by processing with heat a powdered product obtainedby contacting dialkoxymagnesium, diester of an aromatic dicarboxylicacid, aromatic hydrocarbon, and titanium halide one another, anorganoaluminum compound, and an organosilicon compound.

[0005] JP-A No. 315406/1989 proposes another catalyst for olefinpolymerization and a process for polymerizing olefins in the presence ofthis catalyst. The catalyst for olefin polymerization comprises a solidcatalyst component prepared by causing a suspension containingdiethoxymagnesium and alkylbenzene to contact titanium tetrachloride,reacting the suspension with phthalic acid dichloride, and causing theresulting solid product to contact titanium tetrachloride in thepresence of alkylbenzene, an organoaluminum compound, and anorganosilicon compound.

[0006] JP-A No. 84404/1990 proposes a catalyst for olefin polymerizationcomprising a solid titanium catalyst component containing magnesium,titanium, and halogen as the essential components obtained by contactinga magnesium compound and a titanium compound one another, anorganoaluminum compound catalyst component, and an organosiliconcompound catalyst component containing a cyclopentyl group,cyclopentenyl group, cyclopentadienyl group, or a derivative of thesegroups, as well as a process for polymerizing or copolymerizing olefinsin the presence of this catalyst.

[0007] All of the above-described conventional technologies haveattained excellent results in improving the catalyst activity to enableomission of an ash-removal step for removing catalyst residues such aschlorine and titanium from the formed polymers, improving the yield ofstereoregular polymers, and improving the durability of the catalystactivity during the polymerization.

[0008] However, olefin polymers obtained by polymerizing olefins using acatalyst for olefin polymerization containing this type of highly activecatalyst component, an organoaluminum compound, and an organosiliconcompound have been found to possess a molecular weight distributionnarrower than that of olefin polymers obtained by polymerizing olefinsusing a catalyst for olefin polymerization in which the conventionaltitanium trichloride catalyst component is combined with anorganosilicon compound and, optionally, an electron donor compound asthe third component. The narrow molecular weight distribution leads to alow melting viscoelasticity of the polymer, which gives rise to animpaired outward appearance of the final products (polyolefins). Theapplication of the olefin polymers must be limited to a certain degree.

[0009] Various ideas have been put into practice in an attempt to solvethis problem. One example is using multi-stage polymerization to obtainpolyolefin with a broad molecular weight distribution. However, themulti-stage polymerization involves undesirable features including ahigh cost such as repetition of a complicated polymerization process andreclaiming of a chelating agent used in the polymerization.

[0010] JP-A No. 7703/1991 proposes a process for polymerizing olefins inthe presence of a catalyst for olefin polymerization comprising a solidtitanium catalyst component containing magnesium, titanium, halogen, andan electron donor as the essential components, an organoaluminumcompound, and at least two electron donors (organosilicon compounds).

[0011] The applicants claim that the target polyolefin with a broadmolecular weight distribution can be obtained without requiring acomplicated multi-stage polymerization. However, the requirement ofusing two or more organosilicon compounds as electron donors duringpolymerization makes the process complicated.

[0012] Accordingly, an object of the present invention is to solve theabove problems remaining in the prior art and to provide a catalyst forolefin polymerization and a process for polymerizing olefins, which canproduce olefin polymers having a broad molecular weight distribution bya simple procedure while maintaining high stereoregularity.

DISCLOSURE OF THE INVENTION

[0013] In view of this situation, the inventors of the present inventionhave conducted extensive studies and have found that (1) an olefinpolymer having a broad molecular weight distribution and highstereoregularity can be obtained in a high yield by polymerizing olefinsusing a catalyst comprising a specific solid catalyst component madefrom dialkoxymagnesium, tetravalent titanium halide, and an electrondonor compound as raw materials, an organoaluminum compound, and anaminosilane compound having a specific structure and that (2) thecatalyst of the present invention can overcome the problem of decreasedactivity against hydrogen of the catalyst using a conventionalaminosilane compound as an electron donor compound during thepolymerization, which results in producing high melt flow rate polymers,and the catalyst of the present invention can produce polymers with abroader molecular weight distribution and can exhibit activity againsthydrogen the same as or higher than conventional catalysts, producinghigh melt flow rate polymers. These findings have led to the completionof the present invention.

[0014] Specifically, the present invention provides a catalyst forolefin polymerization comprising:

[0015] (A) a solid catalyst component prepared by contacting (a) adialkoxymagnesium, (b) a tetravalent titanium halide compound, and (c)an electron donor compound to one another,

[0016] (B) an organoaluminum compound of the following formula (1),

R¹ _(p)AlQ_(3−p)  (1)

[0017]  wherein R¹ represents an alkyl group having 1 to 4 carbon atoms,Q represents a hydrogen atom or a halogen atom, and p represents a realnumber satisfying the formula 0<p≦3, and

[0018] (C) an aminosilane compound of the following formula (2),

R²R³Si(OR⁴)₂  (2)

[0019]  wherein R² represents a perhydroquinolino group orperhydroisoquinolino group, R³ represents a perhydroquinolino group,perhydroisoquinolino group, an alkyl group having 1 to 12 carbon atoms,a cycloalkyl group, phenyl group, vinyl group, allyl group, or aralkylgroup, the R³ group being either the same as or different from the R²group, and R⁴ individually represents an alkyl group having 1 to 4carbon atoms, cycloalkyl group, phenyl group, vinyl group, allyl group,or aralkyl group.

[0020] The present invention further provides a process for polymerizingolefins characterized by polymerizing or copolymerizing olefins in thepresence of a catalyst for olefin polymerization comprising:

[0021] (A) a solid catalyst component prepared by contacting (a) adialkoxymagnesium, (b) a tetravalent titanium halide compound, and (c)an electron donor compound to one another,

[0022] (B) an organoaluminum compound of the following formula (1),

R¹ _(p)AlQ_(3-p)  (1)

[0023]  wherein R¹ represents an alkyl group having 1 to 4 carbon atoms,Q represents a hydrogen atom or a halogen atom, and p represents a realnumber satisfying the formula 0<p≦3, and

[0024] (C) an aminosilane compound of the following formula (2)

R²R³Si(OR⁴)₂  (2)

[0025]  wherein R² represents a perhydroquinolino group orperhydroisoquinolino group, R³ represents a perhydroquinolino group,perhydroisoquinolino group, an alkyl group having 1 to 12 carbon atoms,a cycloalkyl group, phenyl group, vinyl group, allyl group, or aralkylgroup, the R³ group being either the same as or different from the R²group, and R⁴ individually represents an alkyl group having 1 to 4carbon atoms, a cycloalkyl group, phenyl group, vinyl group, allylgroup, or aralkyl group.

[0026] The perhydroquinolino group in the formula (2) indicates amonovalent group produced from perhydroquinoline by eliminating onehydrogen atom bonding to the nitrogen atom possessed by theperhydroquinoline. The perhydroisoquinolino group indicates a monovalentgroup produced from perhydroisoquinoline by eliminating one hydrogenatom bonding to the nitrogen atom possessed by the perhydroisoquinoline.The both perhydroquinolino group and perhydroisoquinolino group arerepresented by C₉H₁₆N—, wherein N is a free radical.

BRIEF DESCRIPTION OF THE DRAWINGS

[0027]FIG. 1 is a flowchart showing a process for preparing the catalystcomponent and polymerization catalyst of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0028] As the dialkoxymagnesium (a) (hereinafter may be referred to as“component (a)”) used for preparing the solid catalyst component (A)(hereinafter may be referred to as “component (A)”) in the catalyst forolefin polymerization of the present invention, a compound representedby the formula Mg(OR⁵) (OR⁶), wherein R⁵ and R⁶ individually representan alkyl group having 1 to 10 carbon atoms, is preferable. Specificexamples include dimethoxymagnesium, diethoxymagnesium,dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium,ethoxypropoxymagnesium, and butoxyethoxymagnesium. Of these,diethoxymagnesium is particularly preferable. These dialkoxymagnesiumcompounds may be prepared by reacting metallic magnesium with an alcoholin the presence of a halogen or a halogen-containing metal compound. Theabove dialkoxymagnesium compounds may be used either individually or incombination of two or more.

[0029] The dialkoxymagnesium compound used for preparing the component(A) in the present invention may be in the form of either granules orpowder and either amorphous or spherical in the configuration. Forexample, when spherical dialkoxymagnesium is used, the resulting polymeris in the form of a powder having a more excellent granular form and anarrower particle distribution. This improves handling andprocessability of the polymer powder produced during polymerizationoperation and eliminates problems such as clogging caused by fineparticles contained in the polymer powder.

[0030] The spherical dialkoxymagnesium need not necessarily becompletely spherical, but may be oval or potato-shaped. Specifically,the particles may have a ratio (l/w) of the major axis diameter (l) tothe minor axis diameter (w) usually of 3 or less, preferably of 1 to 2,and more preferably of 1 to 1.5.

[0031] The dialkoxymagnesium with an average particle size of 1 to 200μm can be used. A more preferable average particle size is 5 to 150 μm.In the case of spherical dialkoxymagnesium, the average particle size isusually 1 to 100 μm, preferably 5 to 50 μm, and more preferably 10 to 40μm. A powder having a narrow particle size distribution with a smallfine and coarse powder content is preferably used. Specifically, thecontent of particles with a diameter of 5 μm or less is 20% or less, andpreferably 10% or less. On the other hand, the content of particles witha diameter of 100 μm or more should be 10% or less, and preferably 5% orless. Moreover, the particle size distribution represented by ln(D90/D10), wherein D90 is a particle size of 90% of the integratedparticle size and D10 is a particle size of 10% of the integratedparticle size, is 3 or less, and preferably 2 or less.

[0032] Methods for producing such spherical dialkoxymagnesium aredescribed in, for example, JP-A No. 41832/1983, JP-A No. 51633/1987,JP-A No. 74341/1991, JP-A No. 368391/1992, and JP-A No. 73388/1996.

[0033] The tetravalent titanium halide compound (b) (hereinafter may bereferred to as “component (b)”) used for preparing the component (A) inthe present invention is individually or in combination of two or morecompounds selected from titanium halides and alkoxytitanium halides ofthe formula Ti(OR⁷)_(n)X_(4-n), wherein R⁷ indicates an alkyl grouphaving 1 to 4 carbon atoms, X is a halogen atom, and n is an integer of0≦n≦4.

[0034] Specific examples include, as titanium halides, titaniumtetrahalides such as titanium tetrachloride, titanium tetrabromide, andtitanium tetraiodide and, as alkoxytitanium halides, methoxytitaniumtrichloride, ethoxytitanium trichloride, propoxytitanium trichloride,n-butoxytitanium trichloride, dimethoxytitanium dichloride,diethoxytitanium dichloride, dipropoxytitanium dichloride,di-n-butoxytitanium dichloride, trimethoxytitanium chloride,triethoxytitanium chloride, tripropoxytitanium chloride, andtri-n-butoxytitanium chloride. Of these, titanium tetrahalides arepreferable, with titanium tetrachloride being particularly preferable.These titanium compounds may be used either individually or incombination of two or more.

[0035] The electron donor compound used for preparing the solid catalystcomponent (A) (hereinafter may be simply referred to as “component (c)”)is an organic compound containing an oxygen atom or a nitrogen atom.Alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes,amines, amides, nitriles, isocyanates, and organosilicon compoundscontaining a Si—O—C bond can be given as examples.

[0036] Specific examples include: alcohols such as methanol, ethanol,n-propanol, and 2-ethylhexanol; phenols such as phenol and cresol;ethers such as methyl ether, ethyl ether, propyl ether, butyl ether,amyl ether, diphenyl ether, 9,9-bis(methoxymethyl)fluorene, and2-isopropyl-2-isopentyl-1,3-dimethoxypropane; monocarboxylic acid esterssuch as methyl formate, ethyl acetate, vinyl acetate, propyl acetate,octyl acetate, cyclohexyl acetate, ethyl propionate, ethyl butyrate,methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octylbenzoate, cyclohexyl benzoate, phenyl benzoate, methyl p-toluate, ethylp-toluate, methyl anisate, and ethyl anisate; dicarboxylic acid esterssuch as diethyl maleate, dibutyl maleate, dimethyl adipate, diethyladipate, dipropyl adipate, dibutyl adipate, diisodecyl adipate, dioctyladipate, dimethyl phthalate, diethyl phthalate, dipropyl phthalate,dibutyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptylphthalate, dioctyl phthalate, dinonyl phthalate, and didecyl phthalate;ketones such as acetone, methyl ethyl ketone, methyl butyl ketone,acetophenone, and benzophenone; acid halides such as phthalic aciddichloride and terephthalic acid dichloride; aldehydes such asacetaldehyde, propionaldehyde, octylaldehyde, and benzaldehyde; aminessuch as methylamine, ethylamine, tributylamine, piperidine, aniline, andpyridine; amides such as oleic acid amide and stearic acid amide;nitriles such as acetonitrile, benzonitrile, and tolunitrile; andisocyanates such as methyl isocyanate and ethyl isocyanate.

[0037] As examples of the organosilicon compound having an Si—O—C bond,phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane,cycloalkylalkoxysilane, and cycloalkylalkylalkoxysilane can be given.

[0038] Of these electron donor compounds, esters, particularly diestersof an aromatic dicarboxylic acid are preferable, with phthalic aciddiesters and phthalic acid diester derivatives being ideal compounds.Specific examples of the phthalic acid diester include the followingcompounds: dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate,diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,ethylmethyl phthalate, methyl(isopropyl) phthalate, ethyl(n-propyl)phthalate, ethyl(n-butyl) phthalate, ethyl(isobutyl) phthalate,di-n-pentyl phthalate, diisopentyl phthalate, dineopentyl phthalate,dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate,bis(2,2-dimethylhexyl) phthalate, bis(2-ethylhexyl) phthalate,di-n-nonyl phthalate, diisodecyl phthalate, bis(2,2-dimethylheptyl)phthalate, n-butyl(isohexyl) phthalate, n-butyl(2-ethylhexyl) phthalate,n-pentylhexyl phthalate, n-pentyl(isohexyl) phthalate, isopentyl(heptyl)phthalate, n-pentyl(2-ethylhexyl) phthalate, n-pentyl(isononyl)phthalate, isopentyl(n-decyl) phthalate, n-pentylundecyl phthalate,isopentyl(isohexyl) phthalate, n-hexyl(2,2-dimethylhexyl) phthalate,n-hexyl(2-ethylhexyl) phthalate, n-hexyl(isononyl) phthalate,n-hexyl(n-decyl) phthalate, n-heptyl(2-ethylhexyl) phthalate,n-heptyl(isononyl) phthalate, n-heptyl(neodecyl) phthalate, and2-ethylhexyl(isononyl) phthalate. One or more of these compounds can beused.

[0039] As the phthalic acid diester derivatives, compounds derived fromphthalic acid diesters by replacing one or two hydrogen atoms on thebenzene ring, to which the two alkoxycarbonyl groups of the phthalicacid diester bond, with an alkyl group having 1 to 5 carbon atoms or ahalogen atom such as a chlorine, bromine, or fluorine are preferablyused. The catalyst for olefin polymerization obtained by combining thesolid catalyst component prepared by using these phthalic acid diesterderivatives as the electron donor compound (c) can remarkably broadenthe molecular weight distribution of the polymer, as well as increasethe melt flow rate of the polymer due to the high activity or highresponse of the solid catalyst component against hydrogen even in theuse of a smaller or equivalent amount of hydrogen during thepolymerization. As specific examples, dineopentyl 4-methylphthalate,dineopentyl 4-ethylphthalate, dineopentyl 4,5-dimethylphthalate,dineopentyl 4,5-diethylphthalate, diethyl 4-chlorophthalate, di-n-butyl4-chlorophthalate, dineopentyl 4-chlorophthalate, diisobutyl4-chlorophthalate, diisohexyl 4-chlorophthalate, diisooctyl4-chlorophthalate, diethyl 4-bromophthalate, di-n-butyl4-bromophthalate, dineopentyl 4-bromophthalate, diisobutyl4-bromophthalate, diisohexyl 4-bromophthalate, diisooctyl4-bromophthalate, diethyl 4,5-dichlorophthalate, di-n-butyl4,5-dichlorophthalate, diisohexyl 4,5-dichlorophthalate, and diisooctyl4,5-dichlorophthalate can be given. Of these, dineopentyl4-bromophthalate, di-n-butyl 4-bromophthalate, and diisobutyl4-bromophthalate are preferable.

[0040] The above ester compounds are preferably used in combination oftwo or more. In this instance, the esters are preferably combined sothat the total carbon atom number in the alkyl group possessed by oneester may differ four or more from that possessed by another ester.

[0041] The component (A) of the present invention can be preferablyprepared by contacting the above components (a), (b), and (c) oneanother in an aromatic hydrocarbon (d) (hereinafter may be simplyreferred to as “component (d)”). Aromatic hydrocarbons having a boilingpoint of 50° C. to 150° C. such as toluene, xylene, and ethylbenzene arepreferably used as the component (d). These aromatic hydrocarbons can beused either individually or in combination of two or more.

[0042] In addition to the above components (a) to (c) and, optionally,the component (d), a polysiloxane (hereinafter may be simply referred toas “component (e)”) can be desirably used for preparing the solidcatalyst component (A) of the present invention. The use of the catalystof the present invention containing the solid catalyst componentprepared by using a polysiloxane can ensure a broader molecular weightdistribution and improve stereoregularity or crystalinity of theresulting polymer, as well as reduce fine powder in the polymer. It isalso desirable to use the polysiloxane (e) for preparing the solidcatalyst component (A) in addition to the above component (a), thecomponent (b), phthalic acid diester derivatives given as examples ofthe component (c), and the component (d). A polysiloxane is a polymerpossessing siloxane bonds (—Si—O—) in the main chain. Polysiloxanes aregenerally called silicone oil. Those used in the present invention arechain-structured, partially hydrogenated, cyclic, or denaturedpolysiloxanes which are liquids or viscous substances at normaltemperatures with a viscosity at 25° C. in the range of 2 to 10,000 cSt,and preferably in the range of 3 to 500 cSt.

[0043] As examples of the chain-structured polysiloxane,dimethylpolysiloxane and methylphenylpolysiloxane can be given; asexamples of the partially hydrogenated polysiloxane, methyl hydrogenpolysiloxanes with a hydrogenation degree of 10 to 80% can be given; asexamples of the cyclic polysiloxane, hexamethylcyclotrisiloxane,octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane,2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethylcyclotetrasiloxanecan be given; as examples of the modified polysiloxane, higher fattyacid group-substituted dimethylsiloxane, epoxy group-substituteddimethylsiloxane, and polyoxyalkylene group-substituted dimethylsiloxanecan be given. Of these, decamethylcyclopentasiloxane anddimethylpolysiloxane are preferable, with decamethylcyclopentasiloxanebeing particularly preferable.

[0044] In addition to the above essential components, an aluminumcompound (f) such as aluminum trichloride, diethoxyaluminum chloride,diisopropoxyaluminum chloride, ethoxyaluminum dichloride,isopropoxyaluminum dichloride, butoxyaluminum dichloride, ortriethoxyaluminum can be used for preparing the solid catalyst component(A) for olefin polymerization of the present invention. Such an aluminumcompound (f) may be hereinafter referred to as “component (f)”. Ofthese, aluminum trichloride is preferable. The use of a solid catalystcomponent prepared by using this aluminum compound ensures production ofolefin polymers having not only a broader molecular weight distribution,but also reasonably high stereoregularity even with a high isoblockcontent. Such polymers are particularly suitable for fabricating sheetsand films. In addition, if the component (f) and component (e) are usedtogether with the components (a) to (c), and preferably together withthe components (a) to (d), for preparing the solid catalyst component(A), the molecular weight distribution of the produced polymers can beremarkably broadened. It is also desirable to use the component (f) andcomponent (e) for preparing the solid catalyst component (A) togetherwith the component (a), component (b), a phthalic acid diesterderivative as the component (c), and the component (d). When using theabove aluminum compound for preparing the solid catalyst component (A),the aluminum compound (f) is preferably added in the presence of thecomponent (B).

[0045] The process for preparing the component (A) of the presentinvention will now be described.

[0046] One specific example of the process for preparing the solidcomponent (A) comprises suspending the dialkoxymagnesium compound (a) inan alcohol, a halogenated hydrocarbon solvent, the tetravalent titaniumhalide (b), or the aromatic hydrocarbon (d), and causing the electrondonor compound (c) such as a phthalic acid diester and/or thetetravalent titanium halide (b) to contact the suspension. A sphericalsolid catalyst component with a narrow particle size distribution can beobtained by this process using a spherical magnesium compound. Such aspherical solid catalyst component with a narrow particle sizedistribution can also be obtained without using a spherical magnesiumcompound if particles are formed by a spray dry method in which asolution or suspension is sprayed and dried using a sprayer, forexample.

[0047] These components contact one another in a vessel equipped with astirrer in an inert gas atmosphere from which water and the like havebeen removed while stirring. The contact, temperature, which is atemperature when these components are caused to contact, may be eitherthe same as or different from the reaction temperature. When thecomponents contact one another by stirring for preparing the mixture orare dispersed or suspended for a denaturing treatment, the componentsmay be stirred, dispersed, or suspended at a comparatively lowtemperature of around room temperature. When a reaction product is to beobtained by reacting the components after the contact, the componentsare preferably stirred in a temperature range of 40° C. to 130° C. Thereaction does not sufficiently proceed at a reaction temperature below40° C., resulting in a solid component with inadequate properties. Onthe other hand, control of the reaction becomes difficult at atemperature above 130° C. due to significant vaporization of the solventand the like. The reaction time is one minute or more, preferably tenminutes or more, and still more preferably 30 minutes or more.

[0048] As preferable processes for preparing the solid catalystcomponent (A) of the present invention, a process comprising suspendingthe component (a) in the component (d), causing the resulting suspensionto contact the component (b), then the component (c), and causing thesecomponents to react, and a process comprising suspending the component(a) in the component (d), causing the resulting suspension to contactthe component (c), then the component (b), and causing these componentsto react can be given. When the component (e) is used for preparing thesolid catalyst component (A), a process of suspending the component (a)in the component (d), causing the suspension to contact the component(b) and component (c) in an optional order, causing the component (e) tocontact the resulting mixture, then causing these components to react ispreferably employed. When the component (f) is used for preparing thesolid catalyst component (A), a process of suspending the component (a)and component (f) in the component (d), causing the resulting suspensionto contact the component (b) and component (c) in an optional order, andcausing these components to react is preferably employed. Even in thecase of using the component (f), it is possible to cause the component(e) to contact the mixture obtained by causing the component (b) andcomponent (c) to contact the suspension in an optional order, and thencausing these components to react.

[0049] The following examples are given more specifically as thepreferable order of contacting the components one another for preparingthe solid catalyst component (A) of the present invention.

[0050] (1) (a)→(d)→(b)→(c)→<<intermediate washing→(d)→(b)>>→finalwashing→solid catalyst component (A)

[0051] (2) (a)→(d)→(c)→(b)→<<intermediate washing→(d)→(b)>>→finalwashing→solid catalyst component (A)

[0052] (3) (a)→(d)→(b)→(c)→<<intermediate washing→(d)→(b)→(c)>>→finalwashing→solid catalyst component (A)

[0053] (4) (a)→(d)→(b)→(c)→<<intermediate washing→(d)→(c)→(b)>>→finalwashing→solid catalyst component (A)

[0054] (5) (a)→(d)→(c)→(b)→<<intermediate washing→(d)→(b)→(c)>>→finalwashing→solid catalyst component (A)

[0055] (6) (a)→(d)→(c)→(b)→<<intermediate washing→(d)→(c)→(b)>>→finalwashing→solid catalyst component (A)

[0056] (7) (a)→(d)→(b)→(c)→(e)→<<intermediate washing→(d)→(b)>>→finalwashing→solid catalyst component (A)

[0057] (8) (a)→(d)→(c)→(b)→(e)→<<intermediate washing→(d)→(b)>>→finalwashing→solid catalyst component (A)

[0058] The catalyst activity can be further improved if the steps in thedouble parentheses << >> in the above processes of contact are repeatedseveral times, if required. The components (b) and (d) used in the stepsin the double parentheses << >> may be either newly added components orresidues from the previous steps. In addition to the washing stepsindicated in the above processes (1) to (8), the intermediate productsin any of the above contact steps may be washed with a hydrocarboncompound which is liquid at normal temperatures.

[0059] Based on the above description, a particularly preferable processfor preparing the solid catalyst component (A) comprises suspending thedialkoxymagnesium compound (a) or the dialkoxymagnesium compound (a) andthe component (f) in the aromatic hydrocarbon (d) having a boiling pointof 50° C. to 150° C., causing the tetravalent titanium halide (b) tocontact the suspension, and reacting the mixture. In the above process,one or more electron donor compounds (c) such as phthalic acid diestersare caused to contact the suspension at a temperature of −20° C. to 130°C., either before or after the tetravalent titanium halide (b) iscontacted, the electron donor compound (c) is further caused to contact,and the linear or cyclic polysiloxane (e) is caused to contact at atemperature of 20° C. to 130° C. Then, the mixture is reacted to obtaina solid reaction product (1). In this instance, it is desirable to carryout an aging reaction at a low temperature either before or after theabove one or more electron donor compounds (c) are caused to contact thesuspension. After washing the solid reaction product (1) with ahydrocarbon compound which is liquid at normal temperatures(intermediate washing), the tetravalent titanium halide (b) is againcaused to contact the solid reaction product (1) in the presence of anaromatic hydrocarbon compound at a temperature of −20° C. to 100° C., toobtain a solid reaction product (2). As required, the intermediatewashing and the reaction may be further repeated several times. Whenreacting the mixture after again causing the tetravalent titanium halidecompound (b) to contact, the electron donor compound (c) maybe caused tocontact together. Next, the solid reaction product (2) is washed with ahydrocarbon compound which is liquid at normal temperatures (finalwashing) to obtain the solid catalyst component (A).

[0060] Preferable conditions of the above reactions and washingoperations are as follows.

[0061] Low temperature aging reaction: −20° C. to 70° C., preferably−10° C. to 60° C., and more preferably 0° C. to 30° C., for 1 minute to6 hours, preferably 5 minutes to 4 hours, and particularly preferably 10minutes to 3 hours.

[0062] Reaction: 40° C. to 130° C., preferably 70° C. to 120° C., andparticularly preferably 80° C. to 115° C., for 0.5 to 6 hours,preferably 0.5 to 5 hours, and particularly preferably 1 to 4 hours.

[0063] Washing: at 0° C. to 110° C., preferably 30° C. to 100° C., andmore preferably 30° C. to 90° C., from 1 to 20 times, preferably 1 to 15times, and particularly preferably 1 to 10 times. Hydrocarbons used forwashing are preferably aromatic hydrocarbons or saturated hydrocarbonswhich are liquid at normal temperatures. Specific examples includearomatic hydrocarbons such as toluene, xylene, and ethylbenzene, andsaturated hydrocarbons such as hexane, heptane, and cyclohexane. Thearomatic hydrocarbons are preferably used for the intermediate washing,whereas the saturated hydrocarbons are preferably used for the finalwashing.

[0064] The ratio of the compounds used for preparing the solid catalystcomponent (A) cannot be generically defined, because such a ratio variesaccording to the process employed. For example, the tetravalent titaniumhalide (b) is used in an amount of 0.5 to 100 mols, preferably 0.5 to 50mols, still more preferably 1 to 10 mols; the electron donor compound(c) is used in an amount of 0.01 to 10 mols, preferably 0.01 to 1 mol,and still more preferably 0.02 to 0.6 mol; the aromatic hydrocarbons (d)are used in an amount of 0.001 to 500 mols, preferably 0.001 to 100mols, and still more preferably 0.005 to 10 mols; the polysiloxane (e)is used in an amount of 0.01 to 100 g, preferably 0.05 to 80 g, andstill more preferably to 50 g; and the aluminum compound (f) is used inan amount of 0.01 to 10 mols, preferably 0.05 to 5 mols, and still morepreferably 0.1 to 1 mol; for one mol of the dialkoxymagnesium (a).

[0065] There are also no specific limitations to the amount of titanium,magnesium, halogen atoms, and electron donor compounds in the solidcatalyst component (A) of the present invention. The content of titaniumis 1.0 to 8.0 wt %, preferably 2.0 to 8.0 wt %, and still morepreferably 3.0 to 8.0 wt %; the content of magnesium is 10 to 70 wt %,preferably 10 to 50 wt %, more preferably 15 to 40 wt %, andparticularly preferably 15 to 25 wt %; the content of halogen atoms is20 to 90 wt %, preferably 30 to 85 wt %, more preferably 40 to 80 wt %,and particularly preferably 45 to 75 wt %; and the total amount ofelectron donor compounds is 0.5 to 30 wt %, preferably 1 to 25 wt %, andparticularly preferably 2 to 20 wt %.

[0066] There are no specific limitations to the organoaluminum compound(B) (hereinafter may be simply referred to as “component (B)”) used forpreparing the catalyst for olefin polymerization of the presentinvention, inasmuch as the compound has a structure of the above formula(1). In the formula (1), an ethyl group and isobutyl group arepreferable as R¹, a hydrogen atom, chlorine atom, and bromine atom arepreferable as Q, and p is preferably an integer of 2 or 3, andparticularly preferably 3. As specific examples of such anorganoaluminum compound (B), triethylaluminum, diethylaluminum chloride,triisobutylaluminum, diethylaluminum bromide, and diethylaluminumhydride can be given. These compounds may be used either individually orin combination of two or more. Triethylaluminum and triisobutylaluminumare preferably used.

[0067] The compounds represented by the above formula (2) can be givenas the aminosilane compound (C) (hereinafter may be simply referred toas “component (C)”) which can be used for preparing the catalyst forolefin polymerization of the present invention. The amino silanecompound has a silicon atom to which the nitrogen atom of aperhydroquinolino group or perhydroisoquinolino group bonds. Specificexamples of the aminosilane compound includebis(perhydroquinolino)dialkoxysilane,bis(perhydroisoquinolino)dialkoxysilane,perhydroquinolinoalkyldialkoxysilane, andperhydroisoquinolinoalkyldialkoxysilane. Among the compounds representedby the above formula (2), those having the same group for R² and R³ arepreferable, with a compound having the same group for R², R³, and R⁴being particularly preferable. A perhydroisoquinolino group isparticularly preferable as R². As R⁴, an alkyl group having 1 to 4carbon atoms is preferable, with a methyl group being particularlypreferable.

[0068] Specific examples include the following compounds:bis(perhydroquinolino)dimethoxysilane,bis(perhydroquinolino)diethoxysilane,bis(perhydroisoquinolino)dimethoxysilane,bis(perhydroisoquinolino)diethoxysilane,ethyl(perhydroquinolino)dimethoxysilane,ethyl(perhydroisoquinolino)dimethoxysilane,n-propyl(perhydroquinolino)dimethoxysilane,n-propyl(perhydroisoquinolino)dimethoxysilane,isopropyl(perhydroquinolino)dimethoxysilane,isopropyl(perhydroisoquinolino)dimethoxysilane,butyl(perhydroquinolino)dimethoxysilane,butyl(perhydroisoquinolino)dimethoxysilane,isopropyl(perhydroquinolino)dimethoxysilane,isopropyl(perhydroisoquinolino)dimethoxysilane,t-butyl(perhydroquinolino)dimethoxysilane,t-butyl(perhydroisoquinolino)dimethoxysilane,pentyl(perhydroquinolino)dimethoxysilane,pentyl(perhydroisoquinolino)dimethoxysilane,isopentyl(perhydroquinolino)dimethoxysilane,isopentyl(perhydroisoquinolino)dimethoxysilane,cyclopentyl(perhydroquinolino)dimethoxysilane,cyclopentyl(perhydroisoquinolino)dimethoxysilane,cyclohexyl(perhydroquinolino)dimethoxysilane,cyclohexyl(perhydroisoquinolino)dimethoxysilane,phenyl(perhydroquinolino)dimethoxysilane, andphenyl(perhydroisoquinolino)dimethoxysilane. These compounds may be usedeither individually or in combination of two or more. Of these, bis(perhydroquinolino)dimethoxysilane andbis(perhydroisoquinolino)dimethoxysilane are preferable.

[0069] In addition to the above components, an organosilicon compoundother than the above-described aminosilane compound (hereinafter may besimply referred to as “component (D)”) may be used for preparing thecatalyst for olefin polymerization of the present invention. As anexample of such an organosilicon compound (D), a compound of thefollowing formula (3) can be given.

R⁸ _(q)Si(OR⁹)_(4-q)  (3)

[0070] wherein R⁸ individually represents an alkyl group having 1 to 12carbon atoms, cycloalkyl group, phenyl group, vinyl group, allyl group,or aralkyl group, R⁹ individually represents an alkyl group having 1 to4 carbon atoms, cycloalkyl group, phenyl group, vinyl group, allylgroup, or aralkyl group, and q is an integer satisfying an inequality of0≦q≦3. As specific examples, phenylalkoxysilane, alkylalkoxysilane,phenylalkylalkoxysilane, cycloalkylalkoxysilane, andcycloalkylalkylalkoxysilane can be given.

[0071] As more specific examples of the above organosilicon compound(D), di-n-propyldimethoxysilane, diisopropyldimethoxysilane,di-n-butyldimethoxysilane, diisobutyldimethoxysilane,di-t-butyldimethoxysilane, di-n-butyldiethoxysilane,t-butyltrimethoxysilane, dicyclohexyldimethoxysilane,dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane,cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane,cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane,dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane,cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane,cyclohexylcyclopentyldimethoxysilane,cyclohexylcyclopentyldiethoxysilane,3-methylcyclohexylcyclopentyldimethoxysilane,4-methylcyclohexylcyclopentyldimethoxysilane, and3,5-dimethylcyclohexylcyclopentyldimethoxysilane can be given. Theseorganosilicon compounds (D) can be used individually or in a combinationof two or more.

[0072] In the case where the above components (D) are used incombination, the preferable combinations with the above components (C)are as shown in Table 1. TABLE 1 Component (C) Component (D) (1)Bis(perhydroisoquinolino) Diisopropyldimethoxysilane dimethoxysilane (2)Bis(perhydroisoquinolino) Diisobutyldimethoxysilane dimethoxysilane (3)Bis(perhydroisoquinolino) Cyclohexylmethyldimethoxysilanedimethoxysilane (4) Bis(perhydroisoquinolino)Dicyclopentyldimethoxysilane dimethoxysilane (5)Bis(perhydroisoquinolino) Cyclohexylcyclopentyldimethoxysilanedimethoxysilane

[0073] Olefins can be polymerized or copolymerized using the catalystfor olefin polymerization of the present invention. As olefins,ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like can be used either individually or incombination of two or more. Of these, ethylene, propylene, and 1-butenecan be suitably used. A particularly preferable olefin is propylene.Propylene may be copolymerized with other olefins. As olefins to becopolymerized, ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like can be used either individually or incombination of two or more. Of these, ethylene and 1-butene can besuitably used.

[0074] The ratio of each component used is not specifically limitedinasmuch as such a ratio does not influence the effect of the presentinvention. Usually, the component (B) is used in the amount of 1 to 2000mols, and preferably 50 to 1000 mols, per one mol of titanium atom inthe component (A). The component (C) is used in the amount of 0.002 to10 mols, preferably 0.01 to 2 mols, and particularly preferably 0.01 to0.5 mols, per one mol of the component (B). If the component (D) is usedin combination, the amount is 0.002 to 10 mols, preferably 0.01 to 2mols, and particularly preferably 0.01 to 0.5 mols, per one mol of thecomponent (B) and 0.01 to 100 mols, preferably 0.1 to 10 mols, andparticularly preferably 0.1 to 1 mol, per one mol of the component (C).

[0075] Although the order of contact of these components is optional, itis desirable to first add the organoaluminum compound (B) to thepolymerization system, then cause the amino silane compound (C) or amixture of the components (C) and (D) to contact the organoaluminumcompound (B), or cause the component (C) and component (D) in anoptional order to contact the organoaluminum compound (B), and cause thesolid catalyst component (A) to contact the resulting mixture. A methodof forming a catalyst by adding the organoaluminum compound (B) to thepolymerization system, separately causing the component (A) to contactthe component (C) or the components (C) and (D), and feeding thecontacted component (A) and component (C) or the components (C) and (D)to the polymerization system is also a preferable embodiment. It ispossible to further improve the catalyst activity against hydrogen andcrystalline properties of the resulting polymer by using a previouslycontacted mixture of the component (A) and component (C) or thecomponents (C) and (D).

[0076] The polymerization of the present invention can be carried outeither in the presence or in the absence of an organic solvent. Olefinmonomers such as propylene may be used either in a gaseous state or in aliquid state. The polymerization reaction is preferably carried out at atemperature of 200° C. or less, and preferably at 100° C. or less, undera pressure of 10 MPa or less, and preferably 5 MPa or less. Either acontinuous polymerization system or a batch polymerization system maybeused for the polymerization reaction. In addition, the polymerizationcan be completed either in one step or in two or more steps.

[0077] In polymerizing olefins using the catalyst containing thecomponent (A), component (B), and component (C) (hereinafter may bereferred to as “main polymerization”), it is desirable to proceedprepolymerization of the olefins prior to the main polymerization tofurther improve the catalyst activity, stereoregularity, properties ofresulting polymer particles, and the like. In addition to the olefinsused in the main polymerization, monomers such as styrene can be used inthe preliminary polymerization. Specifically, after causing thecomponent (A) to contact the component (B) and/or the component (C) inthe presence of olefins to prepolymerize 0.1 to 100 g of the polyolefinsfor 1 g of the component (A), the component (B) and/or the component (C)are further caused to contact to form the catalyst. In the case wherethe component (D) is used in combination, it is possible to cause thecomponent (A) to contact the components (B) and (D) in the presence ofolefins during the prepolymerization and to use the component (C) duringthe main polymerization.

[0078] Although the order of contact of the components and monomers incarrying out the prepolymerization is optional, it is desirable to firstadd the component (B) to the prepolymerization system in an inert gas orolefin gas atmosphere such as propylene, cause the component (A) tocontact the component (B), and then cause one or more olefins such aspropylene to contact the mixture.

[0079] The polymerization of olefins in the presence of the catalyst forolefin polymerization prepared by the process of the present inventioncan produce olefin polymers with a molecular weight distribution broaderthan that of the polymers produced using a conventional catalyst. Inaddition, the catalyst for olefin polymerization of the presentinvention exhibits the same performance as conventional catalysts incatalyst activity and the capability of producing polymers with highstereoregularity. Specifically, the catalyst of the present inventionhas been confirmed to produce polymers with a broader molecular weightdistribution, while maintaining the catalyst activity and crystallineproperties of the polymers.

EXAMPLES

[0080] The present invention will be described in more detail byexamples, which should not be construed as limiting the presentinvention.

Example 1

[0081] (Preparation of Solid Catalyst Component)

[0082] A 2,000 ml round bottom flask equipped with a stirrer, of whichthe internal atmosphere had been sufficiently replaced by nitrogen gas,was charged with 150 g of diethoxymagnesium and 750 ml toluene toprepare a suspension. The suspension was added to a solution of 450 mlof toluene and 300 ml of titanium tetrachloride in another 2,000 mlround bottom flask equipped with a stirrer, of which the internalatmosphere had been sufficiently replaced by nitrogen gas. Thesuspension was reacted at 5° C. for one hour (low temperature agingprocess). After the addition of 22.5 ml of di-n-butyl phthalate, themixture was heated to 90° C. and reacted for two hours with stirring(first process). After the reaction, the resulting reaction mixture waswashed four times with 1,300 ml of toluene at 80° C. (intermediatewashing). After the addition of 1,200 ml of toluene and 300 ml oftitanium tetrachloride, the reaction mixture was heated to 112° C. andreacted for two hours with stirring (second process). The intermediatewashing and second process were repeated once more. The resultingreaction mixture was washed seven times with 1,300 ml of heptane at 40°C., filtered, and dried to obtain a solid catalyst component (A) in theform of a powder. The content of titanium in the solid catalystcomponent was analyzed and found to be 2.9 wt %.

[0083] (Preparation of Polymerization Catalyst and Polymerization)

[0084] A 2.0 l autoclave equipped with a stirrer, of which the internalatmosphere had been entirely replaced by nitrogen gas, was charged with1.32 mmol of triethylaluminum, 0.13 mmol ofbis(perhydroisoquinolino)dimethoxysilane, and the above solid catalystcomponent (A), in terms of the titanium atom contained therein, in anamount of 0.0026 mmol, thereby forming a polymerization catalyst. Then,with the addition of 2.0 l of hydrogen gas and 1.4 l of liquidpropylene, the prepolymerization was carried out for 5 minutes at 20°C., followed by heating the prepolymerized product, and the mainpolymerization was carried out for one hour at 70° C. The polymerizationactivity per 1 g of the solid catalyst component was calculatedaccording to the following formula.

Polymerization activity=Produced polymer (F)(g)/Solid catalyst component(g)

[0085] The polymer (G) insoluble in n-heptane determined by extractingthis polymer for 6 hours in boiling n-heptane was measured to determinethe proportion of components insoluble in boiling n-heptane (HI) in thispolymer according to the following formula.

HI=(G)(g)/(F)(g)

[0086] Xylene soluble components (XS) in the polymer were determined asfollows. Method for measuring xylene soluble components: 4.0 g of thepolymer was added to 200 ml of p-xylene and dissolved while maintainingthe mixture at the boiling point (138° C.) over two hours. The mixturewas cooled to 23° C. and the soluble matters were separated frominsoluble matters by filtration. The soluble components were dried withheating, and the polymer thus obtained was determined as xylene solublecomponents (wt %). The melt index (MI) of the polymer was determinedaccording to the test method conforming to ASTM D1238 or JIS K7210.

[0087] (Molecular Weight Distribution of Polymer)

[0088] The molecular weight distribution of polymers was evaluated bythe ratio (Mw/Mn) of the weight average molecular weight (Mw) to thenumber average molecular weight (Mn) and the ratio (Mz/Mw) of theZ-average molecular weight (Mz) to the weight average molecular weight(Mw), measured by cross fractionation chromatography (CFC) using CFCT-150B (manufactured by Mitsubishi Chemical Corp.) under the followingconditions.

[0089] Solvent: o-dichlorobenzene (ODCB)

[0090] Temperature: 143° C. (SEC)

[0091] Column: Shodex GPC UT-806M

[0092] Sample concentration: 4 g/l-ODCB (200 mg/50 ml-ODCB)

[0093] Charge amount: 0.5 ml

[0094] Flow rate: 1.0 ml/min

[0095] Temperature: 0° C. to 140° C.

[0096] (Measurement of Polydispersity Index (PI))

[0097] Polydispersity index (PI) was measured using a dynamic stressrheometer (DSR) using SR-500 manufactured by Rheometric Scientific, Inc.Additives described below were added to samples to prevent the samplesfrom becoming deteriorated due to heat.

[0098] Measurement mode: Frequency sweeping mode

[0099] Temperature: 200° C.

[0100] Stress: 2,000 dyn/cm²

[0101] Frequency range: 100 to 0.1 rad/sec.

[0102] Additive: A slurry prepared by mixing 4 g of2,6-dibutyl-p-cresol, 8 g of DLTP (Lasmit), 2 g of calcium stearate, 6 gof Mark 260 (ADK STAB), and 200 ml or more of acetone was added to thepolymers in the following ratio.

[0103] Ratio (slurry/polymer): 5 ml/5 g

[0104] Polymerization activity, heptane insoluble (HI), melt index (MI),xylene soluble (XS), molecular weight distribution (Mw/Mn) and (Mz/Mw),and polydispersity index (PI) are described in Table 2.

Example 2

[0105] (Preparation of Solid Catalyst Component)

[0106] A 2,000 ml round bottom flask equipped with a stirrer, of whichthe internal atmosphere had been sufficiently replaced by nitrogen gas,was charged with 150 g of diethoxymagnesium and 750 ml toluene toprepare a suspension. The suspension was added to a solution of 450 mlof toluene and 300 ml of titanium tetrachloride in another 2,000 mlround bottom flask equipped with a stirrer, of which the internalatmosphere had been sufficiently replaced by nitrogen gas. Thesuspension was reacted at 5° C. for one hour (low temperature agingprocess) After the addition of 22.5 ml of di-n-butyl phthalate, themixture was heated to 100° C. Then, 30 ml of cyclic polysiloxane(decamethylcyclopentasiloxane “TFS-405” manufactured by GE ToshibaSilicones Co., Ltd.) was added. The mixture was heated to 105° C. andreacted for two hours with stirring (first process). After the reaction,the resulting reaction mixture was washed four times with 1,300 ml oftoluene at 80° C. (intermediate washing). After the addition of 1,200 mlof toluene and 300 ml of titanium tetrachloride, the reaction mixturewas heated to 112° C. and reacted for two hours with stirring (secondprocess) The intermediate washing and second process were repeated oncemore. The resulting reaction mixture was washed seven times with 1,300ml of heptane at 40° C., filtered, and dried to obtain a solid catalystcomponent (A) in the form of a powder. The content of titanium in thesolid catalyst component was analyzed and found to be 3.1 wt %.

[0107] A polymerization catalyst was prepared and polymerization wascarried out in the same manner as in Example 1, except for using thesolid catalyst component prepared above. The molecular weightdistribution of the polymer was evaluated and the polydispersity index(PI) was measured in the same manner as in Example 1. The results areshown in Table 2.

Example 3

[0108] A polymerization catalyst component and a catalyst were preparedand polymerization was carried out in the same manner as in Example 1,except that dineopentyl 4-bromophthalate was used instead of di-n-butylphthalate for preparing the solid catalyst component. The molecularweight distribution of the polymer was evaluated and the polydispersityindex (PI) was measured in the same manner as in Example 1. The resultsare shown in Table 2. The content of titanium in the solid catalystcomponent was analyzed and found to be 2.9 wt %.

Example 4

[0109] (Preparation of Solid Catalyst Component)

[0110] A 500 ml round bottom flask equipped with a stirrer, of which theinternal atmosphere had been sufficiently replaced by nitrogen gas, wascharged with 10 g of diethoxymagnesium, 1.5 g of aluminum trichloride,and 90 ml of toluene to prepare a suspension. After the addition of 22ml of titanium tetrachloride at room temperature, the mixture wasreacted while heating to 80° C. with stirring. Then, 3.3 ml ofdi-n-butyl phthalate and 3.0 ml of dimethylpolysiloxane with a viscosityof 50 cst at room temperature were added. The mixture was heated to 110°C. and reacted for 2 hours (first reaction process). After the reaction,the supernatant liquid was removed and the residue was washed threetimes with 88 ml of toluene at 75° C. 89 ml of toluene and 22 ml oftitanium tetrachloride were added and the mixture was stirred for 1.5hours at 100° C. (second reaction process). The reaction mixture waswashed eight times with 83 ml of n-heptane at 40° C. to obtain a solidcatalyst component. The content of titanium in the solid catalystcomponent was analyzed and found to be 3.3 wt %. The content of aluminumwas 0.5 wt %.

[0111] A polymerization catalyst was prepared and polymerization wascarried out in the same manner as in Example 1, except for using thesolid catalyst component prepared above. The molecular weightdistribution of the polymer was evaluated and the polydispersity index(PI) was measured in the same manner as in Example 1. The results areshown in Table 2.

Comparative Example 1

[0112] A 2,000 ml round bottom flask equipped with a stirrer, of whichthe internal atmosphere had been sufficiently replaced by nitrogen gas,was charged with 95.2 g of magnesium dichloride, 442 ml of decane, and390.6 g of 2-ethylhexyl alcohol. The mixture was reacted at 130° C. fortwo hours to obtain a homogeneous solution. 21.3 g of phthalic anhydridewas added to the solution and the mixture was stirred at 130° C. for onehour to dissolve the phthalic anhydride, thereby obtaining a homogeneoussolution. After cooling to room temperature, 75 ml of the homogeneoussolution was added to 200 ml of titanium tetrachloride. The mixture washeated to 110° C., 5.22 g of diisobutyl phthalate was added, and themixture was reacted for two hours with stirring. After the reaction, thereaction product was suspended again in 275 ml of titanium tetrachlorideand processed for two hours at 110° C. The resulting reaction mixturewas washed seven times with heptane at 40° C., filtered, and dried toobtain a solid catalyst component in the form of a powder. The contentof titanium in the solid catalyst component was analyzed and found to be2.8 wt %. A polymerization catalyst was prepared and polymerization wascarried out in the same manner as in Example 1, except for using thesolid catalyst component prepared above. The molecular weightdistribution of the polymer was evaluated and the polydispersity index(PI) was measured in the same manner as in Example 1. The results areshown in Table 2.

Comparative Example 2

[0113] A polymerization catalyst component and a catalyst were preparedand polymerization was carried out in the same manner as in Example 1,except that cyclohexylmethyldimethoxysilane was used instead ofbis(perhydroisoquinolino)dimethoxysilane for preparing the solidcatalyst component. The molecular weight distribution of the polymer wasevaluated and the polydispersity index (PI) was measured in the samemanner as in Example 1. The results are shown in Table 2. TABLE 2Polymerization Activity HI MI XS Example (g-PP/g-cat.) (wt %) (g/10 min)(wt %) Mw/Mn Mz/Mw PI Example 1 43500 98.3 7.0 1.6 12.9 14.1 8.0 Example2 43500 98.5 6.5 1.4 10.5 13.2 7.5 Example 3 46300 97.8 13 2.0 14.2 50.47.9 Example 4 41700 96.5 9.5 3.5 15.3 51.1 8.2 Comparative 35400 98.14.5 2.3 9.6 12.9 7.1 Example 1 Comparative 48400 98.2 6.8 1.7 6.6 9.04.3 Example 2

[0114] As can be seen from the above results, polymers produced by usingthe catalyst of the present invention has stereoregularity equivalent toor higher than that of the polymers obtained by conventional catalystsshown in Comparative Examples 1 and 2, as well as a remarkably broadermolecular weight distribution represented by Mw/Mn or Mz/Mw. Inparticular, the high Mz/Mw ratio indicates an increase of polymers in ahigh molecular weight region, resulting in a remarkably broadenedmolecular weight distribution. Furthermore, notwithstanding the broadmolecular weight distribution, the high melt index (MI) possessed by thepolymers prepared in Examples, equivalent to or higher than that of thepolymers produced in Comparative Examples 1 and 2, indicates highactivity against hydrogen of the catalyst.

Industrial Applicability

[0115] Olefin polymers with a broad molecular weight distribution can beobtained by polymerizing olefins using the catalyst of the presentinvention, while maintaining the high stereoregularity of the polymers.Polymers have increased melting viscoelasticity, whereby the problem ofrestricted application due to impaired fabrication properties andappearance of the products can be solved. In addition, the catalystexhibits activity against hydrogen equivalent to or higher than theactivity exhibited by conventional catalysts, whereby polymers with ahigh melt flow rate can be obtained.

1. A catalyst for olefin polymerization comprising: (A) a solid catalystcomponent prepared by contacting (a) a dialkoxymagnesium, (b) atetravalent titanium halide compound, and (c) an electron donor compoundto one another, (B) an organoaluminum compound of the following formula(1), R¹ _(p)AlQ_(3−p)  (1)  wherein R¹ represents an alkyl group having1 to 4 carbon atoms, Q represents a hydrogen atom or a halogen atom, andp represents a real number satisfying the formula 0<p≦3, and (c) anaminosilane compound of the following formula (2), R²R³Si(OR⁴)₂  (2) wherein R² represents a perhydroquinolino group or perhydroisoquinolinogroup, R³ represents a perhydroquinolino group, perhydroisoquinolinogroup, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,phenyl group, vinyl group, allyl group, or aralkyl group, the R³ groupbeing either the same as or different from the R²group, and R⁴individually represents an alkyl group having 1 to 4 carbon atoms, acycloalkyl group, phenyl group, vinyl group, allyl group, or aralkylgroup.
 2. The catalyst for olefin polymerization according to claim 1,wherein the solid catalyst component (A) is prepared by contacting (a) adialkoxymagnesium, (b) a tetravalent titanium halide compound, (c) anelectron donor compound, and (d) an aromatic hydrocarbon to one another.3. The catalyst for olefin polymerization according to claim 1, whereinthe solid catalyst component (A) is prepared by contacting (a) adialkoxymagnesium, (b) a tetravalent titanium halide compound, (c) anelectron donor compound, (d) an aromatic hydrocarbon, and (e) apolysiloxane to one another.
 4. The catalyst for olefin polymerizationaccording to claim 1, wherein the dialkoxymagnesium (a) isdiethoxymagnesium.
 5. The catalyst for olefin polymerization accordingto claim 1, wherein the electron donor compound (c) is a phthalic aciddiester.
 6. The catalyst for olefin polymerization according to claim 1,wherein the electron donor compound (c) is a phthalic acid diesterderivative.
 7. The catalyst for olefin polymerization according to claim6, wherein the phthalic acid diester derivative is 4-bromophthalic aciddiester.
 8. A process for polymerizing olefins characterized bypolymerizing or copolymerizing olefins in the presence of a catalyst forolefin polymerization comprising: (A) a solid catalyst componentprepared by contacting (a) a dialkoxymagnesium, (b) a tetravalenttitanium halide compound, and (c) an electron donor compound to oneanother, (B) an organoaluminum compound of the following formula (1), R¹_(p)AlQ_(3-p)  (1)  wherein R¹ represents an alkyl group having 1 to 4carbon atoms, Q represents a hydrogen atom or a halogen atom, and prepresents a real number satisfying the formula 0<p≦3, and (C) anaminosilane compound of the following formula (2), R²R³Si(OR⁴)₂  (2) wherein R² represents a perhydroquinolino group or perhydroisoquinolinogroup, R³ represents a perhydroquinolino group, perhydroisoquinolinogroup, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group,phenyl group, vinyl group, allyl group, or aralkyl group, the R³ groupbeing either the same as or different from the R² group, and R⁴individually represents an alkyl group having 1 to 4 carbon atoms, acycloalkyl group, phenyl group, vinyl group, allyl group, or aralkylgroup.
 9. The process for polymerizing olefins according to claim 8,wherein the solid catalyst component (A) is prepared by contacting (a) adialkoxymagnesium, (b) a tetravalent titanium halide compound, (c) anelectron donor compound, and (d) an aromatic hydrocarbon to one another.10. The process for polymerizing olefins according to claim 8, whereinthe solid catalyst component (A) is prepared by contacting (a) adialkoxymagnesium, (b) a tetravalent titanium halide compound, (c) anelectron donor compound, (d) an aromatic hydrocarbon, and (e) apolysiloxane to one another.
 11. The process for polymerizing olefinsaccording to claim 8, wherein the dialkoxymagnesium (a) isdiethoxymagnesium.
 12. The process for polymerizing olefins according toclaim 8, wherein the electron donor compound (c) is a phthalic aciddiester.
 13. The process for polymerizing olefins according to claim 8,wherein the electron donor compound (c) is a phthalic acid diesterderivative.
 14. The process for polymerizing olefins according to claim13, wherein the phthalic acid diester derivative is 4-bromophthalic aciddiester.